Dry size



Patented Aug. 8, 1939 UNITED STATES PATENT. OFFICE to Hercules Powder Company,

Wilmington,

Del., a corporation of Delaware No Drawing.

Application November 17, 1937,

Serial No. 175,173

14 Claims. (Cl. 134-21) This invention relates to dry size and more particularly to a dry size made from a paraffin hydrocarbon insoluble resin derived from pine wood.

It is well known in the prior art that a dry size can be made by saponiflcation of rosin with an alkali and subsequent dehydration of the size by heating the rosin size on a drum or by spraying it into heated air. For certain types of paper, however, it has been found that ordinary rosin dry size is not applicable for the best results. Furthermore, it has been found that ordinary rosin size does not impart sufllcient toughness to certain types of paper panel board, which are usually heavily loaded with a sizing agent.

In accordance with my invention a superior sizing product is prepared by the treatment of a resinousproduct of the refining of wood rosin with alkaline materials such as, for example, alkali metal hydroxides, ammonium hydroxide, and alkali metal carbonates. I have found that a size made therefrom has several distinct advantages over a similar size made from rosin. The alum precipitate of a size made from my new product has a higher melting point than one made from ordinary rosin, which is very desirable for certain types of paper. A size made therefrom is tougher and will impart to certain types of pater panel board, which are to be heavily loaded with size, a greater toughness with less brittleness than a rosin size. In addition, my new product has better oil resistance than ordinary rosin size so that my size when applied to paper and board will impart better oil resistance to the material so sized.

There are also advantages in the manufacture of dry size from this resinous product. The saponiflcation thereof requires less of the alkaline materials, before mentioned, than rosin. Furthermore, the reaction between this resinous product and the said alkaline materials is considerably faster than between rosin and the same materials, and hence, there is a higher temperature rise which means that less external heat need be'applied, this being also an economic advantage.

This resinous product of the refining of wood rosin has not been analyzed completely to determine its exact constitution, on account of its extreme chemical complexity. I have, however, determined that such resinous product has a methoxy content of about 3% to about 6%, and contains, among other things, various oxidized resin acids, oxidized terpenes, polyphenols, polymerized terpenes, and complex ligneous substances, but since its exact "composition is so far unknown, I shall'hereinafter define such resin by its method of preparation.

In one method of. preparing the resin, later to be saponified to form my improved size, pine 5. wood, preferably that from Southern Long Leaf Pine, with or without preliminary steaming to remove therefrom turpentine and pine oil, is extracted with a solvent which is a solvent for the wood rosin, turpentine, and pine oil con- 10 tained in the pine wood chips, and which is also a solvent for other complex substances contained in the pine wood chips. Such a solvent may be, for example, a coal tar hydrocarbon, such as benzene, toluene, xylene, etc.

After the wood chips have been sufilciently extracted, the coal tar hydrocarbon solution of matter extracted from the chips is drawn oif, the chips and the solvent re-used in the process, if desired. After evaporating 01f the solvent a 0 residue remains consisting essentially of turpentine, pine oil, rosin and the resin, the saponified form of the latter resin being the object of this invention. After removal of the turpentine and pine oil by distillation, there remains a dark 25 colored resin comprising a mixture of FF rosin and the other resin. This mixture is then extracted with a substance which is a solvent for the FF rosin but not a solvent for the other resin present in the mixture. As such solvents, I prefer 30 using paraflin hydrocarbons such as petroleum ether, gasoline, heptane, hexane, etc., or an operable equivalent therefor.

After sufiicient extraction of the resinous material with the paraffin hydrocarbon, a dark 35 colored resinous substance remains, which, when freed from occluded gasoline or otherlparaflin hydrocarbon, is the resin-I use in the preparation of my improved size. A typical sample of my improved resin will have the following character- 40 istics: A methoxy content of about 3% to 6%, (in contrast to 0.3% to 0.4% methoxy for.an oxidized wood rosin and 0.1% to 0.2% methoxy for a gum rosin), a melting point, A. S. T. M.

drop method, of C., an acid number of 100, 45

and naphtha insoluble matter of 98%.

Hereinafter the term resin will refer to the resin made by the method above described.

In the manufacture of my improved dry size a quantity of the resin, prepared as shown above, 50 is introduced into a reaction vessel where it is heated to the desired temperature, a solution of an alkaline material, such as, for example, alkali metal hydroxides, ammonium hydroxide, and alkali metal carbonates, among which are, for 55 example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, etc., added, and then the resin is saponifled with or without the addition of external heat. The quantity of alkaline material added should be preferably suflicient to saponify the resin completely, although I may add an excess or a deficiency of alkaline material, thereby forming a resin size containing an excess of free alkaline material or an excess of free resin, respectively.

I may also add an antioxidant to the above saponified resin in order to prevent the subsequent oxidation of the size when dry. The antioxidant chosernmay be incorporated at any convenient time during the process of making the size but, generally speaking, I have found that the antioxidant preferably in solution in a suitable solvent therefor is desirably and most effectively incorporated with the size in the reaction vessel in which the size is formed by sa-. ponification of the resin. The amount of antioxidant in any given case may vary widely. Generally, where the size contains the freeresin or the free alkaline material used for saponifying the resin, a larger amount of antioxidant is required than where the size is neutral.

As antioxidants for the resin size, whether or not the size centains some of the free resin or some of the free alkaline material, for example, phenyl-beta-naphthylamine, symmetrical dibeta-naphthyl-para-phenylenediamine, phenylalpha-naphthylamine, azobenzol, hydroxymethylanethol, ditolylamine, diphenylamine, tetramethyldiamino-diphenylmethane, p,p-dimethoxydiphenylamine, and p,p-diphenyl-p-phenylenediamine, di-p-anisyl-p-phenylenediamine, cyclohexylphenylamine, aryltetrahydrophenyl fi naphthylamine and para-aminodiphenylamine will be found effective.

The saponifled resin, with or without antioxidant, as made above, is, of course, wet, and in order to recover the size in the form of discrete particles,'substantially dry, in which form it is easier to handle and more economical to ship, I may spray the wet size into a gaseous medium, e. g., air, the temperature of which is higher than that of the sprayed resin size, or I may superheat the size under pressure and then spray it into a gaseous medium, e. g., air, which is at a temperature below that of the sprayed material, or I may drum dry my improved resin size by passing the same over steam heated drums. When spray drying, the quantity of water used in the saponification vessel should be so chosen, that on spraying the saponified resin into a chamber through which air is circulating, substantially all the water in the sprayed size will be evaporated before the particles settle to the bottom of the chamber.

As a specific example of the preparation ofmy improved dry resin size, I show the following, using both sodium hydroxide and potassium hydroxide as the saponifying agent.

When saponifying with sodium hydroxide the resin is heated to 149-150 C. in an oil jacketed, mechanically agitated reaction vessel and the pressure is increased to a gauge pressure of 80 lbs. by means of compressed air. The oil in the jacket is not allowed to circulate after the resin has reached the above temperature. hydroxide is dissolved in water to a concentration of 39% and this is heated to 132 C. in the alkali injection blowcase. A pressure of 120 to 130 lbs. gauge is then placed on the alkali injection blowcase and the above prepared caustic solution injected into the molten resin.v This injection requires about 25 to 35 seconds during which the pressure in the reaction vessel is maintained between 80 to 90 pounds gauge by means of venting. -As soon as the major reactions have occurred, which will be in approximately 1 minute, the vent is closed and the gauge pressure will rise to 110-120 lbs. due to the temperature rise. The temperature rise due to the caustic alkali injection is about 25 C. "to 30', C. and should cause the reaction vessel temperature to increase to about 175 C. to 180 C. in a few minutes.

Ten minutes after the hydroxide solution, down to the point at a gauge pressure of about 100 lbs. and the the reaction vessel is vented .phenyl ,e-naphthylamine-paraflin oil combination is injected. After an additional 10 minutes in the reaction vessel, the batch is ejected at a temperature of 176 C. to 178 C., circulating oil from a Merrill heating system, in the jacket, if necessary, to maintain this temperature. The pressure at ejection is about 110 lbs. gauge, with no added air pressure on the reaction vessel. The resin size is recovered in the form of discrete particles, substantially dry.

When using potassium hydroxide the procedure is similar to the above except that an aqueous solution of 55% to 60% concentration is used, which is heated to about 150 C. before injection into the resin. In addition a larger amount of the phenyl p-naphthylamine-paraflin oil combination is used.

When using an alkali metal carbonate, such as, for example, sodium carbonate, I operate in a manner similar to the above using equivalent amounts and concentrations of the sodium carbonate. I

A dry size made as described above has several advantages over a dry rosin size. The alum precipitate thereof has a higher melting point which is very desirable for certain types of paper. The size made from my resin has greater toughness so that for certain types of paper panel board, which are heavily loaded with a size, it imparts a greater toughness to such board with less brittleness than a size made from rosin. The size made as just described when applied to paper and board imparts greater oil resistance to the materials so sized.

Where, in the claims, I refer to a paraflln hydrocarbon insoluble resin derived from pine wood,

Thesodiuminjection of the sodium' of foaming, which will occur.

I refer to a resin obtained by extracting pine wood with a coal tar hydrocarbon, removing the volatile substances from the extract obtained, and then extracting the non-volatile residue with a pariffin hydrocarbon, such as, for example,

gasoline, thereby removing the rush: from the extract and recovering the paraflln hydrocarbon insoluble resin.

It will be understood that the details and formulae hereinabove set forth are illustrative only, and that the invention as herein broadly described is in no way limited thereby.

a, cs,s9a What I claim and desire to protectby Letters latent is:

1. A dry size in the form of discrete particles, substantially dry, comprising the saponiflcation product of a paraffln hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates.

2. A dry size in the form of discrete particles, substantially dry, comprising the saponiflcation product of a paramn hydrocarbon insoluble resin derived from pine wood and an alkaline'material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates, and an antioxidant for the said saponified resin.

3. A dry size in the iorni of discrete particles, substantially dry, comprising the saponiflcation product of a parailin hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates, and said resin in unsaponifled form.

4. A dry size in the form of discrete particles, substantially dry, comprising the saponiflcation product of a paramn hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates and said alkaline material in free form.

5. A dry size in the form of discrete particles substantially dry, comprising the saponiflcation product of a paraffin hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates, said resin in unsaponifled form and an antioxidant for the said saponifled and unsaponified resin.

6. A dry size in the form of discrete particles, substantially dry, comprising the saponiflcation product of a paraflin hydrocarbon'in'soluble resin derived from pine wood and sodium hydroxide.

'7. A dry size in the form of discrete particles,

substantially dry, comprising the saponiflcation product of a paraflln hydrocarbon insoluble resin 50 derived from pine wood and potassium hydroxide.

8. A dry size in the form of discrete particles,

- metal carbonates and diphenylamine.

derived from pine wood and an alkaline material metal carbonates, said resin in unsaponifled form,

substantially dry, comprising the saponiflcation product of a paraflin hydrocarbon insoluble resin derived from pine wood and sodium carbonate.

9. A dry size in the form of discrete particles, substantially dry, comprising the saponification product of a parailln hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide, and alkali metal carbonates and phenyl-alpha-naphthylamine. a

10. A dry size in .the form of discrete particles, substantially dry, comprising the saponiflcation product of a paraflln hydrocarbon insoluble resin derived from pine wood and an alkaline 'material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide, and alkali metal carbonates and phenyl-beta-naphthylamine.

' 11. A dry size in the form of discrete particles,- substantially dry, comprising the saponification product of a paraflin hydrocarbon insoluble resin derived from pine wood and an alkaline ma'terial selected from the group consisting of alkali metal hydroxides, ammonium hydroxide, alkali 12. A dry size in the form of discrete particles, substantially dry, comprising the saponiilcatlon product of a paraffin hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates, said resin in unsaponifled form, and phenyl-alpha-naphthylamine. 13. A dry size in the form of discrete particles, substantially dry, comprising the saponiflcation product of a paraiiin hydrocarbon insoluble resin selected from the group consisting of alkali metal hydroxides, ammonium hydroxide and alkali metal carbonates, said resin in unsaponifled form, and phenyl-beta-naphthylamine.

14'; A dry size in the form of discrete particles, substantially dry, comprising the .saponiflcation product of a parailin hydrocarbon insoluble resin derived from pine wood and an alkaline material selected from the group consistins of alkali metal hydroxides, ammonium hydroxide and alkali and diphenylamine.

mm c; 

